Detergent composition



Patented st 2%, 119

DETERGENT COMPOSITION Nathaniel Beverley Tucker, Glendale, Ohio, as-

signor to The Procter & Gamble Company, Cincinnati, Ohio, a corporation of Ohio No Drawing. Application May 24, 1947,- Serial No. 750,371

15 Claims. 1

The present invention relates to detergent compositions, and more particularly to soap-containing compositions which are highly resistant to curd-forming ingredients of hard water.

It is well known that the use of ordinary toilet or household soap in hard water results in the formation and precipitation of insoluble fatty acid salts, more commonly referred to as lime soaps." It is also known that such precipitated lime soaps have a tendency to coagulate and form a sticky curd. This curd is commonly observed in the washstand and bath tub and also in the laundry rinse tub where it rises to the surface of the water as a scum, adheres to the walls of the tub as a ring, and sticks to the clothes during the rinsing operation, thereby giving to the clothes an unsightly, dingy appearance, producing spots upon subsequent ironing, and often causing the development of a rancid odor. When soap is used for shampooing the hair, rinsing with hard water results in deposition of the lime soaps on the hair. In applications as divergent as the dyeing of textile fabrics and the plating of metals, the formation of lime soaps has undesirable effects.

In fact, if soap is used in hard water, insoluble lime soap curd forms during the rinsing proccss or whenever the soap dilution becomes sufficiently great to destroy the foaming and dispersing power of the soap.

The coagulation of the lime soaps to form soap curd is dependent not only on the degree of dilution of the soap in the hard water, but also on the age of the solution and on the degree of violone-e Of agitation to which it is subjected, in-

creasing age and increasing agitation both being important factors in promoting coagulation.

The primary object of the present invention is to provide a soap composition which forms little or no lime soap curd when used with hard water.

Another object is to provide a detergent composition which will not form a sticky lime soap curd which will cling to clothes or form the unslghtly, difiicultly removable soap ring in the washstand or bathtub.

A further object is to increase the resistance of soap-containing detergent compositions to precipitation of lime soap and the coagulation thereof to form curd when such compositions are used in hard water under conditions involving prolonged standing or agitation.

It is known that synthetic detergents such as various organic sulfonates and sulfates, and certain other Organic sulfuric acid derivatives, when mixed or used with soap in hard water are capable of reducing the formation of lime soap curd. Several such mixtures have been proposed. Some have been commercially produced and designated as hard water soaps, allegedly free of curd forming characteristics when used in hard water. However, according to my investigations and experience, products prepared in accordance with prior art practices, even those which contain more synthetic detergent than soap, frequently form objectionable curd in hard water under normal conditions of use. As the proportion of synthetic detergent increases, the trouble with such hard water curd may decrease in seriousness, but at the same time the cost of the product increases and some of the desirable physical properties found in soap are adversely affected.

As more fully hereinafter described, I have discovered that certain aliphatic carboxylic acid amides of the primary amines, 1,3-aminodioxaneand its homologs (although possessing no p wer to inhibit curd formation when used with soap alone) have a marked power to inhibit lime soap precipitation and curd formation in the case of curd-forming detergent compositions comprising essentially a mixture of soap and synthetic detergent in proportions more fully hereinafter described. This power exists even when the compositions are used under conditions wherein the solution is subjected to prolonged standing or to mild or vigorous agitation.

I am aware that prior workers in the art have suggested the combination of soap with synthetic detergents (Patents 1,906,484, 2,026,816 and 2,088,308). Also attention is called to my recently issued patent covering the use of above noted amides with synthetic detergents to improve the sudsing and detergent power thereof (Patent 2,383,739). None of these patents, however, suggests the use of such amides for inhibiting the curd formation when compositions comprising soap and synthetic detergent are employed in hard water.

Amides which come within the scope of the invention are carboxylic amides of the formula:

where RC0 is the acyl radical of a'saturated or unsaturated aliphatic carboxylic acid having from about 10 to about 25 carbon atoms, R is selected from the group consisting of hydrogen,

CnHuCON-C CH:

CH| O Launmlde of -amino-L3-dioxane CHr-O CnHnCO-NCCH on,

CHr-O Lauramlde of 5-amlno-5-methyl-1,3-dioxane CH|-O C| nC0N--CC:H; CH1

CHr-O Capramide of 5-amino-5-ethyl-1,3-dioxane CHa-O CuHnC0-N-CCHaOH CH| CHr-O Myriatamide of 5-amino-5-methylol-1,3-dioxane cm-o CuHaCO-N-C-CH! CH-CH:

CHr-O Lam-amide of 5-amlno-2,5-dlmethyl-1,3-dloxane H-O CI1HIICONCCHIOH\CHCHS CHI-O Olelc acid amide of 5-amino-5-methylol-2,4,6-trimethyl- 1,3-dioxane CHr-O CnHhCO-N-C-CHzON CHC;H1

CHr-O Stenamide of 5-amlno-5-methylol-2-propyl-1,3-dloxane CHa-O CnHaCON-CC;H1 CH1 CHa-O Lauramlde of 5-amino-5-propyl-1,3-dioxane GHQ-O CuHnCO-N-CCHOH CH:

Hr-O

Lauramide of fi-amino-fi-alphahydroxyethyl-1,3-dloxane CH; CH;

C() CnHnCO-N-O CHa 0-0 13 \CHI Lluramide of lS-amlno4,4,6-trimetbyl-1,3-dloxane CH; CH!

C0 CnHuCO-,NC CH-CHa C CHg Lani-amide of IS-amino-2,4,4,6,6pentamethyl-1,3-dioxane Lauramlde of 5-amlno-4,4,6-trlmethyl-5-alpha-hydroxyethyl-1,3-dloxane Instead of employing amides of single carboxylic acids as above indicated, amides of mixtures of aliphatic carboxylic acids, especially those mixtures derived from oils, fats, and waxes of animal and vegetable origin, may be employed without departing from the spirit of the invention. For example, amides of a mixture of higher fatty acids derived from oils of the coconut oil group (a group of tropical nut oils characterized by their high content of lauric and myristic acids) such as coconut oil, palm kernel oil, and babassu oil are of particular value. Corresponding amides of mixtures of other fatty acids derived from other oils and fats such as palm oil, tallow, cottonseed oil, sunflower seed oil, fish oils such as menhaden oil and the like, as well as hydrogenated and partially hydrogenated fats and oils in general, also may be employed. Corresponding amides of synthetic aliphatic carboxylic acids having 10 to 25 carbon atoms may also be used. Such carboxylic acids may be obtained, for example, by oxidation of paraflin hydrocarbons or petroleum, or they may be obtained directly by hydrogenation of carbon monoxide (sometimes referred to as the Fischer-Tropsch process) or indirectly by oxidation of the saturated or unsaturated hydrocarbons or oxygenated hydrocarbons resulting from this process.

The kind of soap which is used in preparing my improved detergent compositions is not a limitation of the invention. Any of the watersoluble soaps formulated for industrial, household, and toilet use may be employed. Thus the character of the soap constituent may vary widely in its composition depending on whether the final ternary composition is to be in powdered, spray dried, flake, bar, paste, thread, liquid or other form, and it is to be understood that the specific soaps referred to in the examples given below and prepared from tallow and coconut oil are not to be construed as limiting in nature. Water-soluble soaps such as the sodium soaps and other suitable alkali metal or ammonium soaps derived from other fats and oils such as cottonseed oil, soybean oil, corn oil, olive oil, palm oil, peanut oil, palm kernel oil, lard, greases, fish oils and the like as well as their hydrogenated derivatives, and mixtures thereof, properly blended to yield the desired soap quality, may be used in compounding the ternary mixtures herein contemplated.

The synthetic detergent constituent of the present detergent compositions may be broadly designated as a detergent of the class consisting of water-soluble salts of organic sulfonic acids and water-soluble salts of aliphatic sulfuric acid esters, that is, water-soluble salts of organic sulfurlc reaction products having in the molecular structure a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals. As indicated above in the designation of the soap which may be used in compounding the compositions of my invention, the choice of synthetic detergent will depend inter alia on the physical characteristics of the final product,

annoys that is, whether the composition is to be in flake, bar, paste, or other form. Obviously if a detergent composition in bar form is desired, it will be impractical to combine ingredients which are too soft to retain their shaped form in use.

Snythetic detergents of special interest and particular value are the water-soluble salts of higher alkyl sulfuric acids containing from 8 to 18 carbon atoms in the alkyl radical. More specifically, the alkali metal salts of sulfuric acid esters of normal primary aliphatic alcohols having 10 to 18 carbon atoms, particularly those whose principal active ingredient is a watersoluble salt of lauryl sulfuric acid or oleyl sulfuric acid, have proved of value in compounding products of the present invention. Thus the sodium salt of alkyl sulfuric acids obtained from the mixed higher alcohols derived by the reduction of coconut oil, palm kernel oil, babassu oil, or other oils of the coconut oil group or the sodium alkyl sulfate derived from sperm oil alcohols may be employed. In addition, water-soluble alkyl sulfates having pronounced detergent power and derived from high molcular branched chain primary alcohols or from high molecular secondary alcohols may be used.

Other aliphatic sulfuric acid esters which may be employed in the preparation of detergent compositions of the present invention include watersoluble salts of sulfuric acid esters of polyhydrlc alcohols incompletely esterifled with high molecular weight soap-forming carboxylic acids. Such synthetic detergents include the water-soluble salts of sulfuric acid esters of higher molecular weight fatty acid monoglycerides such as sodium salt of the coconut oil fatty acid mono-ester of l,Z-dihydroxy-propane-3-sulfuric acid ester, triethanolamine salt of mono-oleoyl diethylene glycol sulfate, sodium mono-myristoyl ethylene glycol sulfate, and sodium mono-lauroyl diglycerol sulfate.

Similarly water-soluble salts of ethers of high molecular weight normal primary alcohols and lower molecular weight hydroxy alkyl sulfuric acid esters may be employed. Specific examples of such synthetic detergents are sodium salt of mono fatty-alcohol-of-coconut-oil ether of glycerol-monosulfuric acid and sodium salt of lauryl ether of ethylene glycol monosuliuric acid.

In addition, sulfuric acid ester synthetic detergents such as water-soluble salts of sulfated higher fatty acid alkanolamides, for example the sodium salt of sulfated coconut oil fatty acid ethanolamide and of sulfated babassu oil fatty acid glycerol amide, may be employed in the practice of the invention.

The amino dioxane amides hereinabove referred to are active also in inhibiting curd formation in the case of those detergent compositions which contain in combination with soap an organic synthetic detergent having a true sulfonate group. These synthetic detergents include salts of higher molecular weight monofatty acid esters of lower molecular weight hydroxy alkyl sulfonic .acids such as the sodium salt of the coconut oil fatty acid monoester of 1,2-dihydroxy-propane- 3-sulfonic acid, and the oleic acid ester of the sodium salt of isethionlc acid. Included also are the higher molecular weight fatty acid amides of lower molecular weight amino alkyl sulfonic acids (for example, sodium and potassium salts of oleic acid amide of N-methyl taurine),' the water-soluble salts of the higher molecular weight alcohol esters of sulfocar-boxylic acids (for example, sodium salt of the lauryl alcohol ester of sulfoacetic acid), lower molecular weight sulfocarboxylic acid amides of alkylolamine esters of higher molecular weight fatty acids (for example, sodium salt of the sulfoacetamide of amino ethyl iaurate), higher alkyiated aryl sulfonlc acids (for example, sodium and potassium salts of the sulfonic acid derived from the condensation product of benzene and a chlorinated kerosene fraction containing predominantly 10 to 14 carbon atoms per molecule such as represented by the formula SOsH in which R- is the alkyl group), and ethers of higher molecular weight alcohols and lower molecular weight hydroxy alkyl sulfonic acids (for example, monolauryl ether of 1,2-dihydroxy-propane-3-sodium sulfonate and monolauryl ether of the sodium salt of isethionlc acid).

Although the essential ingredients of the compositions of the present invention comprise essentially a ternary mixture of amino dioxane amide, soap and synthetic detergent, it will be appreciated that the incorporation in the mixture of additional ingredients commonly used with cleansing compositions, such as perfumes, starch, urea, triethanolamine, inorganic salts (silicates, carbonates, ortho-, meta-, pyro-, and triphosphates and the like), albuminous substances, glycerin, insecticides and germicides and the like, is contemplated as part of the instant invention.

The following example will illustrate the manner in which the invention may be practiced, but

it is to be understood that such details are given merely for exempliflcation purposes and are not to be construed as limiting the scope of the ap-' pended claims. In all instances the proportions are expressed in parts by weight.

Example 1.-Detergent flakes are prepared by milling on soap milling rolls a mixture consisting of '75 parts of a sodium soap derived from 75% tallow and 25% coconut oil and containing about 3% water, 20 parts of a commercial synthetic detergent containing about 88% sodium salt of the sulfuric acid ester of alcohols derived from coconut oil (the remaining 12% being largely NazSOO, 5 parts of the lauric acid amide of 5- amino-5-ethyl-1,3 dioxane, to which mixture about 3 parts of water are added in order to give it good milling consistency on the rolls. The resulting milled ribbons are converted into flake form in known manner. These flakes do not give curd in either the wash water or the rinse water'when used for washing dirty dishes in water of 20 grains of hardness per gallon. The ratio of soap to synthetic in these flakes is about 41:1, and the ratio of synthetic to amide is about 3.5:1.

Example 2.Milled bars are prepared by milling on soap milling rolls a mixture consisting of 50 parts of sodium soap derived from tallow and 20% coconut oil and containing about 15% water, 37.5 parts of a commercial synthetic detergent containing about 88% sodium salt of the sulfuric acid ester of alcohols derived from coconut oil (the remaining 12% being largely NaasOi), and 12.5 parts'of the lauric acid amide of 5-amino-5-methyl-L3 dioxane, to which mixture about 5 parts of water are added for ease of milling. The resulting milled ribbons are then plodded in customary soap-making equipment, and the plodded product is cut and stamped in the form of bars. when these bars are used in the bath tub or washstand they do not form curd or an objectionable soap ring in water of 20 grains of hardness per gallon. The ratio of soap to synthetic in these bars is about 1.3:1, and the ratio of synthetic to amide is about 2.6:1.

Example 3.-A laundry detergent in granular form is made by mixing at about 155 F. in a soap crutcher a mixture consisting of 37 parts of tallow kettle soap containing about 65% real soap, 38.7 parts of a paste made by neutralizing with soda lye a crude alkyl benzene sulfonic acid batch in which the alkyl group is a branched chain of about 12 carbon atoms, said paste'containing about 23.5% sodium alkyl benzene sulfonate, about an equal percentage of Na2So4, the balance being essentially water, 3.3 parts of the amide of the mixed fatty acids of coconut oil with 5-amino-1,3 dioxane, 12.4 parts of commercial sodium silicate containing about 42% silicate'solids the ratio of SiO: to NazO in which is about 2.87:1, 6 parts of sodium pyrophosphate, and 2.6 parts of soda ash. The hot crutcher mix is then spray dried in known manner. The resulting granules can be used for washing family bundles of soiled clothes in water of 7 grains per gallon hardness without formation of objectionable hard-water soap scum in the rinse. The ratio of soap to synthetic in this powder is about 2.6:1, and the ratio of synthetic to amide is about 2.8:1.

Example 4.-A flake detergent is prepared by milling on the soap milling rolls a mixture consisting of 55 parts of a sodium soap derived from 75% tallow and 25% coconut oil and containing about 3% water, 35 parts of a commercial synthetic detergent containing about 62.5% sodium salt of'the sulfuric acid ester of alcohols derived from coconut oil (the remaining 37.5% being essentially NazSO4), and 10 parts of the amide of mixed coconut oil fatty acids with 5-amino-2- prowl-1,3 dioxane, to which mixture about 4 parts of water are added for ease of milling. The resulting milled ribbons are converted into flake form in known manner. These flakes do not give objectionable curd in the rinse water when used for washing silks, woolens and fine fabrics in water of 20 grains per gallon hardness. The ratio of soap to synthetic in these flakes is about 2.4:1 and the ratio of synthetic to amide is about 2.2:1.

Example 5.A flake detergent is prepared by milling on the soap milling rolls a mixture consisting of 65 parts of a sodium soap derived from commercial red oil and containing about 3% water, 27 parts of a synthetic detergent containing 88% sodium salt of the sulfuric acid esters of mixed saturated and unsaturated alcohols derived from sperm oil (the remaining 12% being essentially NaCl), and 8 parts of the oleic acid amide of 5-amino-5-methylol-2,4,6-trimethyl- Lil-dioxane, to which mixture the requisite amount of water is added to give good milling characteristics to the mixture. The resulting milled ribbons are converted-into flake form in known manner. These flakes are suitable for use in the textile industry for treatment of fabrics during their manufacture even in treating baths which contain soap-precipitating salts. The ratio of soap to synthetic in these flakes is about 2.6:1 and the ratio of synthetic to amide is about 3:1.

Example 8.Detergent flakes are prepared by milling on soap milling rolls a mixture consisting of 60 parts of sodium soap derived from tallow and 15% coconut oil and containing about 3% water, 35 parts of a commercial synthetic detergent containing about 62.5% sodium salt of the sulfuric acid ester of alcohols derived from coconut oil (the remaining 37.5% being largely NazSOs), and 5 parts of the lauric acid amide of 5-amino-2,5-dimethyl-1,3-dioxane, to which mixture water is added as needed in order to make coherent ribbons. The milled ribbons are converted into flake form in known manner. The resulting flakes are suitable for general household use where a mild and eflicient cleaning asent is required and can be used in hard water without the formation of objectionable curd in the rinse water. The ratio of soap to synthetic in these flakes is'about 2.7:1, and the ratio of synthetic to amide is about 4.4:1.

Example 7 .Milled bars are prepared by milling on soap milling rolls a mixture consisting of 41.9 parts of sodium soap from tallow and containing about 15% water, 37 parts of the sodium salt of the coconut fatty acid mono-ester of 1,2- dihydroxy-propane-3-sulfonic acid, sometimes referred to as the sodium salt of coconut oil monoglyceride sulfonate, and 21.1 parts of the myristic acid amide of 5-amino-5-methylol-L3- dioxane, to which a little water is added in order to give the desired consistency on the milling rolls. The milled ribbons are plodded in customary soap-making equipment, and the plodded product is cut and stamped in known manner. The bars are suitable for toilet use in hard water without giving objectionable curd or ring around the tub. The ratio of soap to synthetic in these bars is about 0.96:1, and the ratio of synthetic to amide is about 1.8:1.

Example 8.Milled bars are prepared-by milling on soap milling rolls a mixture consisting of 33.5 parts of sodium soap from tallow and containing about 15% water, 38 parts of mono-lauryl ether of 1,2-dihydroxy-propane-3-sodium sulfonate, and 28.5 parts of the myristic acid amide of 5-amino-5-methylol-2-propyl-1,3-dloxane, to which a little water is added to give the proper consistency on the milling rolls. The milled ribbons are plodded in customary soap-making equipment, and the plodded product is cut and stamped into bar form in known manner. The bars may be used for toilet purposes in 20 grain .water without giving objectionable curd or ring around the tub. The ratio of soap to synthetic in these bars is about 0.75:1 and the ratio of synthetic to amide is about 1.3:1.

Example 9.-Milled bars are prepared by milling on soap milling rolls a mixture consisting of 70 parts of sodium soap made from tallow and containing about 15% water, 20 parts of a detergent containing 70% sodium salt of the dodecyl alcohol ester of sulfoacetic acid (the remaining 30% being largely NaCl), and 10 parts of the myristic acid amide of 5-amino-5-methylol-1,3-dioxane, to which mixture a little water may be added if necessary to give proper plasticity and coherence to the ribbons. The milled ribbons are plodded in customary soap-making equipment, and the plodded product is out and stamped in known manner in order to give bars. These bars are suitable for toilet use without the formation of objectionable curd in hard water.

The ratio of soap to synthetic in these bars is about 42:1. and the ratio of synthetic to amide is about 1.4:1.

' taining about of the oleic acid amide of the sodium salt of N-methyl taurine (the remaining 85% being largely water), 3 parts of the amide obtained from the mixed C10 to Gas carboxylic acids resulting from the oxidation of parafnn wax, and B-amino 2,5 dimethyl 1,3 dioxane. The crutched product is dried in soap-making equipment suitable for making a powdered product. The resulting product can be used for washing purposes in grain water without the formation of objectionable curd. The ratio of soap to synthetic in the product is about 0.821, and the ratio of synthetic to amide is about 4.1:1.

Example 11.-Milled bars are prepared by milling on soap milling rolls a mixture consisting of 60 parts of sodium soap made from 70% tallow and coconut oil and containing about 15% water, 22 parts of the sodium salt of the coconut oil fatty acid mono-ester of 1,2-dihydroxy-propane-B-sulfuric acid (sometimes referred to as the sodium salt of sulfated coconut oil monoglyceride), and 18 parts of the capramide of 5- amino-2-propyl-4,6-dimethyl-1,3-dioxane, a little water being added in order to give coherence to the ribbons. The milled ribbons are plodded in customary soap-making equipment, and the plodded product is cut and stamped in bar form in known manner. The resulting bars may be used for toilet use in 20 grain water without forming objectionable curd or ring around the tub. The ratio of soap to synthetic in these bars is about 2.3:1 and the ratio of synthetic to amide is about 1.2:1.

In the above examples, reference has been made to use in water of 20 grains of hardness per gallon. It is to be understood, however, that 20 grain water is referred to only as being representative of hard waters in general. According to my experience and investigations, my ternary detergent composition is effective in hard water of any municipal water system or any domestically used water source of which I am aware.

Besides possessing resistance to curd formation in hard water, products of the present invention dissolve at a desirable rate in the water, suds profusely, and cleanse efliciently. Addition of the amino dioxane amide to the soap-synthetic detergent mixtures, as specified in the application, tends in general to increase the sudsins power of the composition. However, excessive additions of amide are to be avoided, as they detergent present and constitutes at least 2 per may decrease sudsing power, harm the desired A physical properties of the soap bar, flake or other product, and interfere with handling in some of the common soap manufacturing processes.

It is especially noteworthy that the bar products of my invention have a definite advantage over bars consisting predominantly of synthetic detergent in that they do not dissolve too rapidly, do not become soft, are more soap-like in appearance and feel, behave more like soap in processing operations, and produce a lather which is generally similar in structure and feel tothat of soap, being unlike that produced from a synthetic detergent alone.

The amount of amide that can advantageously be used is to a degree dependent upon the nature and amount of synthetic detergent present in the composition. The most useful products result when the amount of amide exceeds one sixth of, but is not greater than, the amount of synthetic cent of the combined weight of soap, synthetic and amide.

Most of the above examples cover compositions in which the ratios of essential ingredients come within preferred ranges: that is, a ratio of soap:synthetic from about %:1 to about 4:1 and a ratio of synthetic:amide from about 1.5:1 to about 6:1. The advantages of my discovery, however, are to be realized even in compositions falling outside the above preferred ranges of proportions and accordingly compositions coming within the ratios of soap:synthetic from about /=:1 to about 8:1 and of syntheticzamide from about 1:1 to about 10:1 are contemplated as a part of the broad invention, the amide constiuting at least 2 per cent of the combined weights of soap, synthetic and amide. Optimum results in the case of each composition may be realized by adjustment of the ratios used depending on the types of soap, synthetic detergent and amide employed.

As indicated above, the physical form of the compositions is not a limitation of the invention and may be varied in well known manner. In some instances, however, it may be necessary to adjust temperature conditions or moisture content of the mixture to give a product ofthe desired consistency for handling in the various processing operations required in the development of the desired physical form. Such adjustments of course are well within the scope of those skilled in the art.

The manner of mixing the ingredients is not a limitation of the invention. Any suitable mixing device such as a series of milling rolls ordinarily used in mixing plastic soap with added ingredients or' crutching mechanism of high mixing efficiency as employed in mixing more fluid constituents may be employed to effect homogeneity in the mixture of amide, soap, and synthetic detergent.

Having thus described my invention, what I claim and desire to secure by Letters Patent is:

1. A detergent composition characterized by reduced tendency to form lime soap curd when used in hard water at rinsing dilutions, comprising essentially a ternary mixture of a watersoluble soap, a water-soluble salt of an organic sulfuric reaction product having pronounced detergent properties and having in its molecular structure a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and an'amide of the formula C(R")(R")O/ n" wherein RC0 is the acyl radical of an aliphatic carboxylic acid having from'about 10 to about 25 carbon atoms, R is selected from the group consisting of hydrogen, methyl, methylol, ethyl, alpha hydroxyethyl, and propyl and each R" is selected from the group consisting of hydrogen, methyl, ethyl, and propyl, the sum of the number of carbon atoms in R and all of the R"s being not greater than 5, the ratio of soapzsulfuric reaction product salt being from %:1 to 8:1 and the ratio of sulfuric reaction product saltzamide being from 1:1 to 10:1, and the amount of amide constituting at least 2 per cent of the combined weights of soap, sulfuric reaction product salt, and amide.

2. A detergent composition characterized by reduced tendency to form lime curd when used in hard water at rinsing dilutions, comprising essentially a ternary mixture of a water-soluble soap, a water-soluble salt of an organic sulfuric reaction product having pronounced detergent properties and having in its molecular structure a radical selected from the group consisting of sulfonic acid and sulfuric acid ester radicals, and an amide of the formula C(RII)(RII) O RCONCR c c n") a") o \R" wherein RC is the acyl radical of an aliphatic carboxylic acid having from about to about 25 carbon atoms, R is selected from the group consisting of hydrogen, methyl, methylol, ethyl, alpha hydroxyethyl, and propyl and each R" is selected from the group consisting of hydrogen, methyl, ethyl, and propyl, the sum of the number ofcarbon atoms in R and all of the Rs being not greater than 5, the ratio of soap:sulfuric reaction product salt being from 2/3: 1 to 4:1 and the ratio of sulfuric reaction product saltzamide being from 1%:1 to 6:1.

3. The composition of claim 1 in which the acyl radical RCO of the amide represents the fatty acid residue of mixed high molecular fatty acids of naturally occurring fatty matter.

4. The composition of claim 1 in which the acyl radical RCO of the amide represents the mixed fatty acid residue of an oil the group consisting of coconut, palm kernel and babassu oils.

5. The composition of claim 1 in which the acyl radical RCO of the amide represents the fatty acid residue of the mixed fatty acids of coconut oil.

6. The composition of claim 1 in which the acyl radical RCO of the amide represents the fatty acid residue of a fatty acid having from 10 to 14 carbon atoms.

7. The composition of claim 1 in which the organic sulfuric reaction product salt is a watersoluble salt of an alkyl sulfuric acid having from 10 to 18 carbon atoms in the alkyl radical.

8. The composition of claim 1 in which the sulfuric reaction product salt is a water-soluble salt of alkyl sulfuric acids of higher alcohols derived from an oil of the group consisting of coconut, palm kernel and babassu oils.

9. The composition of claim 1 in which the sulfuric reaction product salt consists of a watersoluble salt of dodecyl sulfuric acid and in which the amide is 11. The composition of claim 1 in which the sulfuric reaction product salt consists of a watersoluble salt of dodecyl sulfuric acid and in which the amide is wherein RCO represents the acyl radical of a saturated fatty acid having 10 to 14 carbon atoms.

12. The composition of claim 1 in which the' SOzH in which R is an alkyl group of from 10 to bon atoms.

15. A detergent composition characterized by reduced tendency to form lime soap curd when used in hard water at rinsing dilutions, comprising essentially a ternary mixture of a water- 14 carsoluble soap, a water-soluble salt of an alkyl sulfuric acid having from 10 to 18 carbon atoms in the alkyl radical, and an amide of the formula wherein RCO represents the mixed fatty acid residue of an oil of the group consisting of coconut, palm kernel and babassu oils, R is selected from the group consisting of hydrogen, methyl, methylol, ethyl, alpha hydroxyethyl, and propyl and each R" is selected from the group consisting of hydrogen, methyl, ethyl, and propyl, the sum of the number of carbon atoms in R and all of the R"s being not greater than 5, the ratio of soapzsulfuric reaction product salt being from V2 1 to 8:1 and the ratio of sulfuric reaction product saltzamide being from 1:1 to 10:1, and the amount of amide constituting at least 2 per cent of the combined weights of soap, sulfuric reaction product salt, and amide.

NATHANIEL BEVERLEY TUCKER.

REFERENCES CITED The following references are of record in the file of this patent:

UNITED STATES PATENTS Number Name Date 2,026,816 Bertsch Jan. '7, 1936 2,303,212 Kise et a1 Nov. 24, 1942 2,383,739 Tucker Aug. 28, 1945 FOREIGN PATENTS Number Country Date 436,866 Great Britain Oct. 16, 1935 Certificate of Correction Patent No. 2,527,078 October 24, 1950 NATHANIEL BEVERLEY TUCKER It is hereby certified that error appears in the printed specification of the above numbered patent requiring correction as follows:

Column 2, in the formula, lower portion thereof, for

read 5 column 3, ninth formula, for that portion thereof reading "-C-CHOH on." -o-oHoH 0H, CHI read \CH: Hr-O III-- last formula, same column, lower portion thereof, for

column 4, in the formula, for that portion thereof reading "CnHzsCONC-CHOH on," OuHnCONC-CHOH on.

05 or, if

and that the said Letters Patent should be read as corrected above, so that the same may conform to the record of the case in the Patent Oflice. Signed and sealed this 23rd day of January, A. D. 1951.

THOMAS F. MURPHY,

Assistant Commissioner of Patents. 

1. A DETERGENT COMPOSITION CHARACTERIZED BY REDUCED TENDENCY TO FORM LIME SOAP CURD WHEN USED IN HARD WATER AT RINSING DILUTIONS, COMPRISING ESSENTIALLY A TERNARY MIXTURE OF A WATERSOLUBLE SOAP, A WATER-SOLUBLE SALT OF AN ORGANIC SULFURIC REACTIONPRODUCT HAVING PRONOUNCED DETERGENT PROPERTIES AND HAVING IN ITS MOLECULAR STRUCTURE A RADICAL SELECTED FROM THE GROUP CONSISTING OF SULFONIC ACID AND SULFURIC ACID ESTER RADICALS, AND AN AMIDE OF THE FORMULA 